Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D1/00—Evaporating
  • B01D1/28—Evaporating with vapour compression
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/007—Energy recuperation; Heat pumps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/10—Vacuum distillation
  • B01D3/106—Vacuum distillation with the use of a pump for creating vacuum and for removing the distillate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/14—Fractional distillation or use of a fractionation or rectification column
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1418—Recovery of products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1493—Selection of liquid materials for use as absorbents
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/22—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/102—Nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/40—Nitrogen compounds
  • B01D2257/402—Dinitrogen oxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
  • B01D2257/702—Hydrocarbons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
  • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2200/00—Processes or apparatus using separation by rectification
  • F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2200/00—Processes or apparatus using separation by rectification
  • F25J2200/50—Processes or apparatus using separation by rectification using multiple (re-)boiler-condensers at different heights of the column
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2200/00—Processes or apparatus using separation by rectification
  • F25J2200/76—Refluxing the column with condensed overhead gas being cycled in a quasi-closed loop refrigeration cycle
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2205/00—Processes or apparatus using other separation and/or other processing means
  • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2205/00—Processes or apparatus using other separation and/or other processing means
  • F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2210/00—Processes characterised by the type or other details of the feed stream
  • F25J2210/80—Carbon dioxide
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2215/00—Processes characterised by the type or other details of the product stream
  • F25J2215/80—Carbon dioxide
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
  • F25J2220/80—Separating impurities from carbon dioxide, e.g. H2O or water-soluble contaminants
  • F25J2220/84—Separating high boiling, i.e. less volatile components, e.g. NOx, SOx, H2S
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
  • F25J2230/08—Cold compressor, i.e. suction of the gas at cryogenic temperature and generally without afterstage-cooler
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
  • F25J2230/80—Processes or apparatus involving steps for increasing the pressure of gaseous process streams the fluid being carbon dioxide
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
  • F25J2235/80—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being carbon dioxide
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J2250/00—Details related to the use of reboiler-condensers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Definitions

• the present invention relates to an improved method for removing contaminants from a stream substantially comprising carbon dioxide. 5 More specifically, the method comprises the ste p of su bjecti ng the stream to a purification step in which liquid carbon dioxide is used and wherein the waste of carbon dioxide is minimized by generating a pressure difference between two streams in a reboiler.
• Carbon dioxide recovery plants are widely used to clean and/or recover carbon dioxide released e.g . from combustion of hydrocarbons, fermentation and gas processing .
• Another purification step is water scrubbing ; in a water scrubber all water-soluble contaminants are removed from the gaseous source.
• the drawbacks of using a water scrubber is the large amounts of clean water used and wastewater formed .
• any water present in the gas is absorbed and thereby removed from the gaseous stream .
• any residues of acetaldehyde, volatiles and/or oxygenates are present in the gas, some of these compounds are also removed in a desiccant, depending on the dehydrator used .
• the gas comprises impurities, which are heavily dissolved in carbon dioxide, i.e. primarily non-polar organic compounds and compounds having a boiling point higher than the boiling point of carbon dioxide under the prevailing conditions, these will not be effectively re- moved from the stream using a water scrubber.
• an adsorption filter e.g. activated carbon, must be used.
• the object of the present invention is to provide a method and plant in which all of the above problems have been solved in an improved.
• the present invention relates to a method for removing at least one contaminant from a gaseous feed stream substantially comprising carbon dioxide, said method comprising the step of subjecting the feed stream to a purification step under conditions providing a carbon dioxide enriched gaseous stream and a contaminant rich liquid stream.
• This problem is in its broadest sense solved by purifying a feed stream in a purification column providing at least a contaminant rich liquid stream and a contaminant lean gaseous stream and reboiling the contaminant rich liquid stream providing a gaseous stream and feeding the gaseous stream to the purification column, wherein a pressure difference between the contaminant rich liquid stream and the contaminant lean gaseous stream is provided before the streams enter the reboiler wherein
• the depressurisation is in a particular embodiment obtained by means of a valve.
• the present inventors have found that by circulating the con- taminant lean carbon dioxide stream and compressing and utilizing the energy for re-evaporating the contaminant rich liquid carbon dioxide in the reboiler, very large amounts of liquid carbon dioxide can be reboiled without the consumption of large amounts of externally supplied energy.
• the present invention has several advantages. By increasing the amount of liquid carbon dioxide used as absorbent, the feed stream will be recovered at a much higher degree of purity. By the solution provided the increasing amount of liquid carbon dioxide used does not compromise the overall economy of the method, i.e. the yield and energy consumption.
• the present invention utilizes the differences in pressure between the liquid stream entering the reboiler (i.e. 12) and the gas entering the reboiler (i.e. g2 or g4, depending on the embodiment) .
• This difference in pressure is provided by the compressing means or the compressing means and the valve.
• the effect can be obtained by two alternatives either by (1) inserting the compression step on the contaminant lean gaseous stream, or (2) inserting the compression step on the gase- ous stream effluent from the reboiler combined with a depressurisation step before the contaminant rich liquid enters the reboiler.
• the depressurisation is in this embodiment preferably performed by inserting a valve.
• the l iq u id before the valve has a pressure pi which is hig her than the pressure p 2 of the liquid having passed the valve.
• appl ies to the gas entering the compressor where the gas entering the compressor has the pressure p 2 and the gas leaving the compressor has the pressure pi, which is higher.
• the difference in pressure, whether the stream is liquid or gaseous, is the same.
• the energy contained in the purified gaseous carbon dioxide stream is utilized to recover otherwise wasted carbon dioxide with only little supply of external energy.
• the feed stream may be both l iq uid and gaseous .
• the method preferably comprises the steps bl) compressing the contaminant lean stream (g2) providing a compressed gaseous stream (g4); cl) cooling the compressed gaseous stream (g4) in a reboiler providing at least a product stream (p) and a gaseous stream (g3) ; and d l) feeding the gaseous stream (g3) to the column at the bottom section of the column (alternative 1) .
• the method comprising the steps b2) cooling the contaminant lean stream (g2) in a reboiler provid- ing at least a product stream (p) and a gaseous stream (g 3) ; and c2) compressing the gaseous stream (g3) providing a cooled compressed gaseous strea m (g4') ; d 2) feed ing the cooled com pressed gaseous stream (g4') to the column at the bottom section of the column; and de- pressurising the contaminant rich liquid stream (12) leaving at the bot- torn section of the column before entering the reboiler (alternative 2).
• the purification step will either be an absorption or a rectification process.
• the purification step is a rectification and when the feeding stream is gaseous the purification step is an absorption process.
• the compression step d) is performed according to alternative 1.
• the embodiment of alternative 2 will be less efficient, as the contaminant rich liquid stream (12) leaving the bottom section of the column will be very low consequently the pres- sure difference provided by the valve on that stream will have a minimal effect.
• the compression step d) can be equally performed according alternative 1 and 2, however in an even more preferred embodiment according to alternative 2. This is due to the lower cost of construction and the reduced amount of energy used to compress the smaller volume of the gaseous stream (g3) as compared to the contaminant lean gaseous stream (g2).
• the pressure in the column is normally between 10 and 40 bar, however, other pressures are contemplated, for example if the tempera- ture of the liquid absorbent carbon dioxide is higher than the freezing temperature of water and hydrates, such as gas and liquid hydrates, under the prevailing pressure, the carbon dioxide would also be able to remove water from the stream.
• a preferred temperature range of the gaseous feed stream is 5 to 25° C, more preferred 5 to 15°C, such as 10°C, although temperatures in the range of -40 to 40°C are contemplated if operating at another pressure.
• the dew point temperature of carbon dioxide in the above mentioned pressure range is -40 to +5.5°C; it is within the skill of the art to determine the dew point temperature of carbon dioxide at any given pressure.
• the method of the present invention is particularly useful for removing contaminants having a boiling point higher than the boiling point of carbon dioxide at the prevailing conditions and/or non-polar compounds. These compounds are not effectively removed by other high through put methods.
• Such compounds may be but are not restricted to sulfides, such as hydrogen sulfide, carbonyl sulfides and dimethylsulfide; nitrogen containing compounds, such as N 2 , ammonia and nitrogen dioxide; and hydrocarbons, such as, methane, n-pentane, n-hexane, ben- zene, toluene and oxygen containing hydrocarbons such as dimethyl ether, acetaldehyde, ethyl acetate, acetone, methanol, ethanol, isobu- tanol and n-propanol.
• the method provides a carbon dioxide enriched gaseous stream and a contaminant enriched liquid stream comprising at least 95 % (w/w) of each of the at
• the absorbent liquid carbon dioxide is an externally supplied source of liquid carbon dioxide, particularly preferred partially a stream from the down stream carbon dioxide purifica- tion process.
• the carbon dioxide stream may in this embodiment be distilled liquid carbon dioxide or condensed carbon dioxide.
• the advantage of this embodiment is that the absorbent, which is used in the column, has a high purity; consequently, there will be no accumulation of impurities in the gaseous phase above the purification column. Moreover, the carbon dioxide of higher purity will have improved absorbing properties. This is particularly advantageous in facilities where a potential build up of contaminants occur frequently, even when contaminants are present in smaller amounts. An external supplemental supply of absorbent liquid carbon dioxide is often necessary in the present invention when the volume of absorbent liquid carbon dioxide by far exceeds the volume of the feed stream.
• the ratio of absorbent liquid carbon dioxide to feed stream is 1 : 3 to 10 : 1, preferably 1 : 3 to 3 : 1 such as 1 : 2, 1 : 1, 2 : 1, 3 : 1, 4: 1, 5 : 1, 6 : 1, 7 : 1, 8 : 1 and 9 : 1.
• the ratio may be in the lower end, such as a ratio of 1 : 1 to 5 : 1 also provided in PCT/DK2009/050159.
• the feed stream comprising water is contacted with an agent capable of decreasing the water activity (a water inhibitor, a dehyd rating agent), herein after "the water in hibitor".
• a water inh ibitor is preferably fed in the purification column at a location between the mid section of the purification col- umn a nd a bove the i n let of the feed strea m, when the feed stream is gaseous; in this context mid-sectio n shou ld be u nd occidental notoriousood as bei ng "mid" relative to the height of the column, i .e . the centre part of the intermediate section .
• the temperature at the bottom of the column will be adjusted so that water does not freeze under the prevail- ing cond itions.
• the freezing point of water is significantly reduced why the temperature is no longer as critical .
• the water inhibitor may be fed at the same position as the feed stream or together with the feed stream, depending on the temperature of the feed stream .
• water inhibitor contemplates any agent capable of decreasing the water activity/inhibit water and may be selected from the group consisting of methanol, ethanol, mono ethylene glycol and tri ethylene glycol . Methanol and ethanol are particularly preferred . Due to the low temperature in the purification column, it is desired to select a water inhibitor that has a low viscosity under the prevailing conditions. Furthermore, it is desired to choose water inhibitors that are relatively inexpensive and easy to recover; recovery of the water inhibitor, e.g . methanol and ethanol is within the skill of the art. Ethanol may be preferred, if the process is implemented in a bio-ethanol plant or a similar pla nt in wh ich fermentation ta kes place i .e . where the water inh ibitor, ethanol, is present in the facility so that no external supply of water inhibitor is needed ; thus, the water inhibitor is in a particular preferred embodiment bio-ethanol .
• the feed stream may comprise ethanol when origi- nating from a bio-ethanol prod uction plant or a fermentation process.
• the feed stream may comprise sufficient ethanol to dehydrate the feed stream in the purification column alternatively; additional ethanol/water inhibitor may be added .
• the water is removed by means of a water scavenger, such as ammonia .
• the dehydration is more flexible as the flow of inhibitor may be adjusted depending on the content of water in a stream to be purified .
• the absorbed water and water inhibitor/scavenger is preferably drawn from the purification column at the bottom section of the column along with the contaminant rich liquid stream .
• the contaminant rich liquid stream may also leave the column at a point higher than/above the inlet of the water inhibitor/scavenger into the column, e.g . between the water inhibitor/scavenger inlet and the mid-section of the column, in order to obtain a water inhibitor/scavenger lean carbon dioxide fraction that may be re- turned to the purification column after an evaporation step, e.g . in the reboiler.
• a fraction of the contaminant rich liquid stream comprising the water inhibitor/scavenger and absorbed impurities is circulated in a loop.
• the contaminant rich liquid stream leaving at the bottom section of the purification column is split in two so that a first contaminant rich liquid fraction of the liquid stream (12a) is recirculated to the inlet of pure water inhibitor/scavenger and mixed therewith . This saves consumption of water inhibitor/scavenger in the over all process by exploiting the full ability of the water inhibitor/scavenger to bind water.
• the water content is relatively low as compared to the capability of any of the above mentioned water inhibitors/scavengers to absorb water; therefore looping the water inhibitor/scavenger so that the water in the feed stream is inhibited by the water inhibitor/scavenger m ixed with water, carbon dioxide and impurities as defined in the context of the present invention, will not impair the water inhibiting ability. Rather the ability of the water inhibitor/scavenger to bind water is fully exploited .
• N0 2 could also be absorbed in the l iq u id C0 2 .
• Th is wou ld force the gas phase eq uil ibrium 1 /-0 2 + N O ⁇ - > N0 2 to the rig ht.
• substantial amounts of the NOx's would be removed from the strea m as N0 2 in the l iq u id C0 2 leaving at the bottom of the purification column .
• N0 2 favours liquid carbon dioxide; once substantially pure liquid carbon dioxide is obtained N0 2 is very difficult to separate off.
• gaseous strea ms com prising trace amou nts of NOx's are add itional ly removed there from .
• the methods of the present invention are in a particular embodiment followed by processing the product gaseous carbon dioxide leaving the column and reboiler by optionally heat exchange, optionally filtration, such as using an activated carbon filter, and finally distillation, e.g . flash distillation or condensation, in order to give a pure liquid carbon dioxide product to be stored and sold .
• the method of the invention is performed in two or more consecutive purification steps, such as 2, 3 or 4. Consequently, it is also contemplated that more than one purification unit of the invention are interconnected .
• the method of the present i nvention a lso co nte m p lates the product carbon dioxide directly obtained after purification using the claimed methods.
• upstream purification steps may be present, such as a condensation step in which a carbon dioxide rich gas and l iq u id is obtained followed by the absorption step accord ing to the present invention .
• the present invention provides a carbon dioxide purification unit.
• This unit is particularly useful for operating the method of the present invention .
• a carbon dioxide purification unit comprising a purification column (Al) having a top and a bottom and a section intermediate of the top and the bottom, the purification column having a feeding stream influent (f), a contaminant lean gas purification column effluent (g2) situated at the top part of the column, a liquid carbon dioxide influent (II) situated at the top part of the column, and a contaminant rich liquid column effluent (12) situated at the bottom part of the purification column,
• a reboiler A3 additionally having a waste liquid effluent (13), a product effluent (p), a compressed gaseous influent (g4), and a gas effluent (g3), the gaseous effluent (g3) being connected to the purification column (Al), wherein a compressing means (A2) is inserted between the reboiler (A3) and the purification column (Al) at a position between the contaminant lean gaseous purification column effluent (g2) and the compressed gaseous influent (g4); or
• the contaminant rich liquid effluent (12) is connected to a reboiler (A3) additionally having a waste liquid effluent (13), a product effluent (p), a contaminant lean gas purification column effluent (g2), and a gas effluent (g3), the gas effluent (g3) being connected to a compressing means (A2) inserted between the reboiler (A3) and the purification column (Al) at a position between the gas effluent (g3) and a cooled compressed gaseous influent (g4') and wherein a valve (A4) is positioned between the contaminant rich liquid effluent and the reboiler (A3).
• the purification column may be an absorption or rectification column known in the art, which is suitable for the particular purpose.
• the nature of the purification column depends on whether the feeding gas is liquid or gaseous. When the feeding stream is gaseous the process in the purification column is an absorption process and when the feeding stream is liquid the process in the purification column is a rectification.
• the intermediate section may be a packed section or if a tray type column, trays.
• the feeding influent is situated at the top section of the pu rification column .
• the feed ing stream is liquid and the contaminant rich liquid effluent is connected to a reboiler additionally having a waste liquid effluent, a product effluent, a contaminant lean gas influent, and a gas effluent, the gas effluent being connected to the purification column, wherein a compressing means is inserted between the reboiler and the purification column at a position between the cooled compressed gas purification column effluent and the contaminant lean gaseous influent.
• the feeding influent is situated at the bottom section of the purification column.
• the position of the reboiler and compressor can be both alternatives provided by the invention.
• the contaminant rich liquid effluent (12) situated at the bottom of the column is split in two at a position outside the column and a first contaminant rich liquid effluent (12') is fed to a water inhibitor and/or scavenger influent (10), and a second contaminant rich liquid effluent (12") is disposed.
• This set-up provides for recycling of the water inhibitor and/or scavenger.
• the branching of the pipe allows the stream to proceed in two ways.
• a valve may control the flows in either direction.
• the purification column is further provided with a carbon dioxide effluent (15) situated at a position between the water inhibitor and/or scavenger influent (10) and the liquid carbon dioxide influent (II).
• liquid carbon dioxide, essentially without water inhibitor and/or scavenger may exit the column for further purification, e.g. being recycled to the purification column.
• the feeding gas influent (g l) is connected to a feeding gas source, preferably partially purified carbon dioxide; and/or the product effluent (p) is connected to a carbon dioxide processing unit, such as a heat exchanger and/or a filter and/or a distillation column ; and/or the liquid carbon dioxide influent (I I) is connected to a liquid carbon dioxide reservoir, e.g .
• the distillation column connected to the product effluent; and/or the waste liquid effluent (13) is connected to a waste reservoir and/or the water inhibitor and/or scavenger influent; and/or the water inhibitor and/or scavenger liquid influent (10) is connected to a water inhibitor and/or scavenger reservoir.
• the carbon dioxide effluent (15) is connected to a carbon dioxide purification u nit, such as the purification column (Al) .
• a carbon dioxide purification u nit such as the purification column (Al) .
• Figure 1 is a flow chart embodying the method of the invention where the compression step/means is positioned according to alternative 1.
• Figure 2 is a flow chart embodying the method of the invention where the compression step/means is positioned according to alternative 2.
• Figure 3 is a schematic illustration of a presently preferred embodiment of alternative 1 of the carbon dioxide purification unit of the present invention in which dehydration of the stream is integrated .
• a su bsta ntia l ly p u re C0 2 stream and/or feed stream comprises more than 80 weight-% C0 2 .
• Purification column (Al); Compression means (A2); Reboiler (A3); Valve (A4); condenser (A5); Filter (A6); Condenser/distillation column (A7); Pump (A8); Heat exchanger (A9).
• impurity and contaminant may be used interchangeably having the same meaning in the context of the present invention and both cover undesired substances in a carbon dioxide stream that should be removed.
• water activity reducing agent agent and water inhibitor and/or scavenger may be used interchangeably having the same meaning in the context of the present invention, and all cover a substance that is capable of removing water from a carbon dioxide stream.
• water free or dry gaseous stream is a gaseous stream in which the water content is so low so as not to cause process related problems, such as freezing within pipes, containers etc. More specifically a water free or dry gaseous stream may be defined as a stream wherein the dew point temperature of water under the prevailing process conditions is lower than the temperature of the stream.
• the method of the present invention can be applied in any carbon dioxide recovery process at a point where the pressure of the feed gas is higher than the triple point pressure of carbon dioxide.
• the method is used on a feed gas having a high carbon dioxide content.
• the method can be applied to but is not limited to streams originating from a flue gas, a fermentation gas, petrochemical combustion gases and carbon dioxide from natural sources.
• the method of the present invention will typically be preceded by an amine absorption step option- ally followed by flash distillation, and stripping as described in EP 1 907 319 Bl .
• the flue gas is condensed and subsequently absorbed in a physical absorbing agent as described in EP 1804956 A.
• the method of the pre- sent invention will typically be preceded by compression and optionally drying.
• compression and optionally drying are examples and the invention should not be limited to these specific applications.
• a feed stream f may be liquid or gaseous, with the proviso that the inlet is situated at the top section of the purification column when the feed stream is liquid.
• figure 1 is shown a purification column Al, a compression means A2 and a reboiler A3.
• the streams shown are the feed stream f, a liquid carbon dioxide stream II, a contaminant lean gas stream g2 leaving at the top of the purification column, a contaminant rich liquid stream 12 leaving at the bottom of the purification column, a compressed gaseous stream g4 leaving the compressing means, a gaseous stream g3 leaving the re- boiler, a waste liquid stream 13 leaving the reboiler, and a product stream p, leaving the reboiler.
• the interaction of streams in the reboiler is as follows:
• the colder contaminant rich liquid stream 12 enters the reboiler in which it is heated by the warmer compressed gaseous stream g4.
• the contaminant rich liquid stream 12 turns into the gaseous stream g3 and the waste liquid stream 13 (i.e. the portion of 12 that is not re-evaporated).
• the warmer compressed gaseous stream g4 be- comes the product stream p, which may be liquid, gaseous or both.
• 12 is the contaminant rich liquid carbon dioxide stream comprising the absorbed/washed/scrubbed out contaminants.
• the contaminant rich stream 12 is fed to the reboiler A3 where it is reboiled providing the gaseous stream g3 and the waste liquid 13, which is optionally discarded.
• the contaminant lean gaseous stream g2 is compressed by means of a compressor or blower providing the compressed gas g4, which is fed to the reboiler A3.
• the product stream p may be both gaseous, liquid and a mixture depending on the conditions.
• the product stream may be further purified as desired for example by, but not limited to, heat exchanging and flash distillation and/or condensation to provide high purity liquid carbon dioxide to be stored in a tank or used directly. This high purity liquid dioxide directly obtained by any of the methods is also contem- plated .
• the feed stream f Before entering the purification column Al, the feed stream f may be passed through a filter and/or a heat exchanger in order to condition the feed stream f for entering the purification column .
• the feed stream f may be both gaseous and/or liquid, thus the preconditioning depends on whether a gaseous and/or liquid feed stream is desired .
• the feed stream is gaseous when the method of the invention is part of a complete carbon dioxide production plant.
• a liquid feed stream will most likely be relevant when non-pure carbon dioxide is supplied from an external source and is to be further purified according to the method of the present invention .
• the feed stream f it may be desirable to prepare the feed stream f so that the temperature is well above the dew point temperature of carbon dioxide at the given conditions.
• the pressure in the purification column will typically be around 6 to 25 bar in the food and bever- age i nd ustry, such as between 15 a nd 23 ba r, e .g . 22.8 ba r. In other applications, pressures are, however, also contemplated such as up to 60 bar, e.g . 40 to 55 bar, or even higher.
• the dew point temperature of carbon dioxide at 10 bar is -40°C; therefore, at that pressure the temperature of the stream entering the col umn shou ld preferably be h ig her than this temperature.
• the gaseous feed stream is cooled, and optionally liquefied before entering the purification column ; in this embodiment the contaminant rich liquid stream will comprise a higher amount of carbon dioxide than when the feed stream is gaseous.
• the contaminant lean gaseous stream leaving the purification column is fed to a compressor in which the difference in pressure is provided .
• FIG 2 an embodiment of the present inven- tion is illustrated in which the influent feed stream shown is gaseous.
• the denotations are the same as given in figure 1 it is also contemplated that the feed stream is liquid and would consequently be situated at the top section of the purification column .
• the compressing means is situated after the reboiler so that the gaseous stream g3 is compressed before entering the purification column .
• a valve A4 is placed to de- pressurise the contaminant rich liquid stream 12 before entering the re- boiler, providing the necessary difference in pressure.
• the duty of the compressing means may be lower as compared to the first embodiment. This is due to the lower amount of carbon dioxide passing through in the gaseous stream g3 as compared to the contaminant lean gaseous stream g2.
• a cheaper compressor may be used, e.g . an oil lubricated compressor, as the compressed gaseous stream provided, g4', is immediately purified removing any traces of oil from the stream.
• FIG 3 an embodiment of the present invention is illustrated in which the influent feed stream is gaseous.
• the denotations as given in figures 1 are the same.
• a liquid stream 10 entering the purification column for example at a position above the feeding stream f and below the mid section of the column .
• the stream 10 comprises the water inhibitor and/or scavenger, e.g . methanol, ethanol, monoethyle- neglycol, triethylene-glycol or ammonia and is therefore a water inhibitor/scavenger feed stream . It is also contemplated that 10 is fed together with or at the same position as the feed stream f or is mixed with the feed stream f before entering the column .
• the stream may comprise ethanol and it may not be necessary to add additional water inhibitor to the purification column .
• the feed stream originates from a bioethanol plant or a fermentation process and the water inhibitor is fed together with the feed stream .
• the water inhibitor/scavenger may be fed at any po- sition of the column, however it is preferred that it is fed at the lower section of the column in order to minimize contamination of the contaminant lean gaseous stream g2.
• the contaminant rich liquid stream 12 leaves the column at a position above the inlets of the feed stream and the water inhibitor/scavenger, respective ly .
• I n th is em bod i me nt the waste liquid stream 13 re-enters the column for use in the lower section, where it is used to scrub out impurities of the incoming gaseous streams fed to the lower part of the column Al .
• a first contaminant rich liquid stream 12a is partly recirculated to the column, this recirculation may be omitted .
• the first contaminant rich liquid stream 12a is withdrawn and at least a portion of the stream is fed to the purification column as a split liquid stream 13b.
• a second waste stream, 13a is discarded .
• the split liquid stream 13b may optionally be subjected to a heat exchanging step (not shown), providing, if heated, either a gaseous stream g3a or a gas liquid mixture or, if cooled, the split liquid stream further cooled .
• the provision of the recirculation provides either a higher degree of purity when a liquid stream is provided, i .e.
• the product is further purified by filtrating (A4), optionally through an activated carbon filter, liquefaction by mea ns of a co nd ense r (A5) a nd/o r a d isti l latio n co l u m n (A5' - not shown) providing a condensed/d istil led l iq uid carbon d ioxide stream 16 and the stream of non-condensable gases g6. It is also contemplated that liquid carbon dioxide may be withdrawn at a position above the inlet of the water inhibitor/scavenger and the contaminant rich liquid stream (12) outlet.
• This stream is denoted a carbon dioxide stream 15 (not shown) .
• the advantage of this embodi- ment is that the water inhibitor/scavenger is not contaminated with a n impurity from which the water inhibitor/scavenger cannot be recovered .
• the contaminant rich liquid stream is preferably situated at the lower part of the column .
• the contaminant rich I i q— uid stream 12 leaving the column is split into the streams 12a the first liquid stream and 12" a second liquid stream .
• 12" is fed to a second re- boiler and 12a is mixed with the water inhibitor/scavenger stream 10 and re-enters the col um n in a mixtu re as the water inhibitor/scavenger.
• 12a com prises ca rbon d ioxide, conta m ina nts, water and the water i n h ibi- tor/scavenger strea m .
• Th is looping of the water inhibitor/scavenger is feasible despite the fact that pure inhibitor is mixed with the first liquid stream 12a because pure inhibitor will often have a water binding capacity which exceeds the amount of water present in the feed stream f. Therefore, by looping the liquid stream 12a to the stream 10, both con- sumption of water inhibitor/scavenger and the volume of the first liq uid stream 12a will be reduced, both resulting in overall savings.
• the ratio of the first liquid stream 12a that is mixed with the water inhibitor/scavenger stream 10 to the contaminant rich stream 12 depends on the water inhibitor/scavenger used . The skilled person will be able to determine the optimal ratio .
• the second liquid stream 12" is fed to the reboiler A3 and re-evaporated and purified according to the invention .
• the first liquid stream 12a is fed to the column again, optionally after be- ing re-evaporated, i .e. the stream 12a is not mixed with 10.
• This embodiment may be desirable if unexpectedly large amounts of water are present in the feed stream f, or if the stream 10 is diluted beforehand so that the concentration of water inhibitor/scavenger is low.
• the absorbent liquid carbon dioxide may be fully or partially originating from the gaseous feed stream to be purified.
• This embodi- ment is suitable when the amount of liquid carbon dioxide to be used is relatively low, such as 400-2000 kg/hour, alternatively it can be used as a supplement to externally supplied liquid carbon dioxide, and is particularly used when the feeding stream is gaseous.
• the purification column in which the method is taking place, is provided with a condensing means, preferably in the top section of the column.
• the condensing means preferably in the top section of the column.
• the percentage The feed stream f was fed at the bottom of the purification column Al at a flow of approximately 100 kmole/hour.
• the major component was carbon dioxide contaminated with minor amounts of the components as indicated in the table.
• the liquid absorbent carbon dioxide stream 10 was fed at the top of the purification column at different flow rates in the range 400 - 2000 kg/hour as indicated in the table above.
• the contaminant rich liquid 12 left the purification column at the bottom section and was discarded or re-boiled according to the prior art method and fed to the gaseous feed stream again and fed to the purification column .
• the contaminant lean carbon dioxide enriched stream leaving the column at the top section was stored or further processed before being stored, e.g . by filtration and distillation .
• a feed stream was treated according to the method described in the comparative example.
• a blower i.e. compressing means, was inserted in accordance with alternative 1 according to the present invention.
• internal energy means energy that is neutral to the refrigeration load.
• the internal energy available will increase with the size of the unit.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• General Engineering & Computer Science (AREA)
• Thermal Sciences (AREA)
• Mechanical Engineering (AREA)
• Physics & Mathematics (AREA)
• Gas Separation By Absorption (AREA)
• Treating Waste Gases (AREA)
• Carbon And Carbon Compounds (AREA)

Priority Applications (17)

Applications Claiming Priority (1)

Related Child Applications (2)

Publications (1)

Family

ID=43568064

Family Applications (1)

Country Status (16)

Cited By (2)

Families Citing this family (12)

Citations (5)

Family Cites Families (17)

• 2010
  • 2010-06-17 CN CN201080067400.4A patent/CN102946972B/zh active Active
  • 2010-06-17 MY MYPI2012700914A patent/MY159234A/en unknown
  • 2010-06-17 NZ NZ605796A patent/NZ605796A/en not_active IP Right Cessation
  • 2010-06-17 KR KR1020137000145A patent/KR101663670B1/ko active IP Right Grant
  • 2010-06-17 WO PCT/DK2010/050146 patent/WO2011157268A1/en active Application Filing
  • 2010-06-17 MX MX2012013106A patent/MX2012013106A/es active IP Right Grant
  • 2010-06-17 JP JP2013514553A patent/JP5795366B2/ja not_active Expired - Fee Related
  • 2010-06-17 AU AU2010355553A patent/AU2010355553B2/en not_active Ceased
  • 2010-06-17 US US13/703,660 patent/US20130152628A1/en not_active Abandoned
  • 2010-06-17 BR BR112012031705A patent/BR112012031705A2/pt not_active Application Discontinuation
  • 2010-06-17 DK DK10725006.0T patent/DK2582445T3/en active
  • 2010-06-17 EA EA201291434A patent/EA023224B1/ru not_active IP Right Cessation
  • 2010-06-17 CA CA2801228A patent/CA2801228A1/en not_active Abandoned
  • 2010-06-17 EP EP10725006.0A patent/EP2582445B1/en active Active
• 2011
  • 2011-06-14 AR ARP110102062A patent/AR081924A1/es not_active Application Discontinuation
• 2012
  • 2012-11-22 ZA ZA2012/08786A patent/ZA201208786B/en unknown
• 2017
  • 2017-04-25 US US15/496,644 patent/US11287183B2/en active Active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events